Patent GB-985707-A (GB)
Title: Diazonium compounds of polyhydrodeca borates
Inventor: KNOTH WALTER HARRY
IPC: C01B21/092
Filed: 1963-09-05
Abstract: The invention comprises compounds of the formulae B10H8(N2)2; M[B10H9.N2]b; B10H8. N2.NH3; B10H8-yXy(N2)2; M[B10H9-y.Xy1.N2] and B10H8-yXy.N2NH3, wherein M is a cation, b is equal to the valence of M, X is a monovalent substituent such as F, Cl, Br, I, -OH, -NCO, -CNO, -CNS, -CN, -NH2, -NO2, -NO, -SO3H; y is 0 to 8, y1 is 0 to 9. The cation M may be H+, H3O+, a metal, a metal-ammine complex, NH4+, or NH2-NH3+. B10H8(N2)2 is made by reacting nitrous acid with a compound of the formula M12B10H10, where M1 i a cation, and reducing the product, for example with NaBH4, LiBH4, LiAlH4, Zn/HCl, Fe/HCl, or hydrogen and Pt or Pd catalyst. M21B10H10 is made by reacting decaborane B10H14 with an organic sulphide and reacting the product with liquid ammonia or an amine. M[B10H9N2]b i formed by reacting M12B10H10 with nitrous acid, reducing the product and contacting the soluble product formed with a cation M to form an insoluble salt of the B10H9N2-1 anion. B10H8.N2 NH3 is made by reacting B10H8.(N2)2 with ammonia.  The substituted compounds B10 H8-yXy(N2)2, and B10H8-yXy.N2NH3 are made by reacting B10H8.(N2)2 and B10H8N2NH3 with a reagent capable of introducing the monovalent substituent. Suitable reagents are specified. Detailed examples are given of the preparation of (NH4)2B10H10; H2B10H10; B10H8.(N2)2; CsB10H9.N2; HB10H9.N2; B10H8.N2.N2H4; B10H5Cl3.(N2)2, B10H2I6(N2)2 and other halogenated compounds; and B10H8.2NH3.  Specification 985,706 is referred to.ALSO:The invention comprises compounds of the formula <FORM:0985707/C2/1> where M is an atom or group of atoms forming a cation in aqueous solution; X is a monovalent substituent which can be bonded to a nuclear carbon of a carbocyclic aromatic compound by replacement of hydrogen; Z is one of the following groups -N2, NH3, an amine, a hydrazine, an organic sulphide, a tertiary phosphine, or an amide of a carboxylic acid; n is 0 or 1; y is an integer from 0 to (9-n) and b has a valence of at least 1 and equals the valence of M. Of the compounds represented by Z, the preferred types are R2S, R3P, R3N, R2N-NR2, R2NCHO and R2NCO.CH3, wher the R groups, which can be alike or different, are hydrocarbon radicals of up to 18 carbon atoms or are joined to form a ring with the S, P or N.  X represents a wide range of radicals such as -F, -Cl, -Br, -I, hydrocarbon, -COOH, -CONH2, -CONR2, -CO.Hal, -OH, -OR1, -CH(OR1)2, -CR1 (OR1)2, -OCO.R1, -CO.OR1, NCO, -CNO, -CNS, -CH2OR1, -CH2NR12, -CN, -NH2, -NR2, -CCl3, -CF3, -COR1, -CHO, -NO2, -NO, -N = N-Ar, -SO3H, -SO2R1, -HgOCOCH3, where R1 is a monvalent organic group.  The cation M may be H+, H3O+, a metal, a metal-ammine complex, NH4+, NH2-NH3+, N-substituted ammonium, N-substituted hydrazonium, S-substituted sulphonium, and P-substituted phosphonium.  Compounds of the type B10H8. N2.SR2 are made by reacting M1B10H9.SR2, where M1 is H, NH4, substituted ammonium or an alkali metal with nitrons acid and reducing the product, for example with NaBH4, LiBH4, LiAlH4, Zn/HCl, Fe/HCl, or hydrogen and Pt or Pd catalyst.  M1B10H9.SR2 is made by reacting decaborane B10H4 with an organic sulphide, reacting the product with liquid ammonia or amine to form M12B10H10 and reacting this with a sulphoxide R2S = O.  Compounds of the type B10H8.N2Z are made by reacting B10H8.(N2)2 with ammonia, an amine, a hydrazine, a phosphine, an organic sulphide or an amide of a carboxylic acid. Substituted compounds of the types B10H8- yXy(N2)2, B10H8- yXy N2.SR2 or B10H8- yXy.N2Z are made by reacting B10H8.(N2)2, B10H8.N2.SR2 or B10H8.N2Z with a reagent capable of introducing a monovalent substituent into a benzene nucleus by replacement of hydrogen. Suitable reagents are specified. Compounds of the type M[B10H9.N2]b are made by reacting nitrons acid with M12B10H10, reducing the product and contacting the soluble product formed with a cation M to form an insoluble salt of the B10H9N2-1 anion. Detailed examples are given. Specification 985,706 is referred to.